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ooooooooo SSSSSSS 0F DESULPHRIZ' IIIIIII .l

Patented Aug. 9 1 8 9 Z.

. phur remains in the oil, as it does in both of and JOSIAH Il. MACY, residing at Ilarrison, in

UNITED STATES- PATENT OFFICE.

OTTO P. AMEND, OF NEW YORK, AND Jo'sIAI-I H. MACY, or HARRISON,

. NEW YORK.

PROCESS .OF DESULPHURIZING Oil-.8.

SPEQIFICATION forming part of Letters Patent No. 480,312', dated August 9, 1892.

Original application led February 18, 1892,A Serial No. 421,919. Divided and this application tiled June 10, 1892. Serial No.

436,216. (No specimens.)

To all whom it may concern:

Be it known that we, OTTO P. AMEND, residing at New York, in the county of New York,

the county of Westchester, State of New York,I citizensof the United States, have invented a new and useful Process of Desulphurizing Oils, of which the following is a specification.

It is well known that in the effort to refine petroleum-oilscontainingsulphurcom pounds, as Ohio and Canadian oils, much diculty has been experienced in eliminating the sulphur and in producing an oil that will not show sulphur reaction after au interval of' time. 1I itherto the majority of those attempting to desulphurize oil have mixed one or more chemical ageutswith the oil While in liquid condition, and have depended upon such chemicals to effect an entire elimination of the sulphur present in accordance with what has been supposed to be the usual law of chemical action. In some instances heat has been applied to hasten such action. Me- Ifallic oxides, alkalies, fuming sulphur-ic and nitric acid have been used in this manner without eiecting a satisfactory' result.V Others operating with the same end in View have rst vaporized the oil and then subjected the oil-vapor to the action of Various chemicals in the presence of heat, with abelief that the action of the chemicals upon the oil while in a state of vapor was more satisfactory than when in a liquid condition. In thelatter case the heat applied has been somewhat higher than was necessary to complete adistillation of oil; 'but we aroled to believe that neither of these methods as hitherto applied will so purify the oil that sulphur reaction will not develop after a short interval of time, and .this of necessity must be the case while sulthe cases cited. We have discovered that sulphur and all sulphur compounds can be removed from the above-named Oils, and that sulphur reaction docs not occur in oil treated by a proper process.

We attain the practical desulphurization of oils containing sulphur by vaporizing the oil and subjecting the oilvapor,`together with' ing the sulphur and cracking or splitting up V its compounds and then exposing the vaporized sulphur and its cracked or split-up compounds to-the action of such chemical agents or reagents as they have an ainity for or tosuch as will act upon or will combine with Vthem while in this vaporized, cracked, or splitup condition and then liquefying the oil. When treated as described it Will be found that the sulphurand sulphur compounds have been so changed that practically no sulphur can be found in the oil, and it may be treated for further refinement by any of the wellknown methods of treating petroleum-oils.

The degree of heat yrequired tovaporize sulphur at the pressure of the atmosphere is 440 centgrade,rand we find that the heat needed to effect entirely satisfactory work must, be suiciently above this temperature to insure the entire vaporization of the, sulphur and the cracking and splitting up of the sulphur compounds. t We prefer a red heat clearly ldistinguishable in daylight, and have found temperatures between 7 00 and 1,200 centigrade very successful in practical working. We have established these temperatures by comparing the colors obtained with the colors specified by competent-technical authorityas corresponding to the temperatures named,

the colors ranging from a dark red to a bright orange.

4In an application for Letters Patent filed February 18, 1892, Serial No. 421,919, we stated that we have found many chemical agents that will unite withV sulphur when vaporized and split up, as various metals', 'lheir oxides and sub-oxides, the hydrates-and oxides of the alkalies have also given very 'good-results; but we prefer such agents or reagents as have an oxidizing effect, among which we have found manganese dioxide .and other higher oxid es of manganese, barium peroxide,-

the pipe.

the manganates and permanganates, the chomates and bichromates, chromic iron ore, and binoxide of lead to be very successful.

This applicationis a modification or division of the aforesaid application of February 1S, 1892, and is designed to claim specifically the use of one or more of the alkalies or alkaline earths, as'lime, soda, po'tash, magnesia, barytes, strontia, &c., and their hydrates, (caustics,) or carbonates when used separately or together, and not with a metallic oxide, as claimed in the former application, as we find the alkalies of the forms specified very effect-` ive for combining with the Asulphur in oil,

when used as described.

The process will be fully understood by referring to the accompanying illustrates one means of carrying out our inventon.

The numeral 1 represents a plain still, such as is generally used for distilling oil.

2 is the outlet for oil-vapors passing from the still.

3 is the fire-chamber under the still, and 4 the ash-pit.

5 represents the flue from the still-furnace. It is shown running behind the flue of the auxiliary furnace and side by side with it, yet separated by a partition until they meet at the outlet of each at the smoke-stack 6.

'7 is the pipe that conveys the oil-vapor, with the heated sulphur and sulphur compounds, to the superheater and chemical-box S. rThis box is made of `thick cast-iron and hasa thick pipe 9 cast with it, which projects from one side near the bottom and communicates with the oil-vapor pipe 'i of the still. The box Sis held in position by a heavy iron clamp 10, which rests upon the top of the furnace 11.

The furnace 11 has a return-flue somewhat'V similar to that of a smelting-furnace, with an opening leading from the furnace ,at 12, running thence downward until it is about in line with the main flue 5 from the furnace of the still. It then runs side by side with the flue of the still-furnace. until it opens into the smoke-stack. The` fire-pot of the furnace 11 is quite deep to hold aconsiderable body of fuel, and its sides flare or diverge a little more on the side where pipe 9 is exposed-than lou the other, with a view of heating the pipe very hot. The box is so suspended that its lower part projects into the combustion-chamber of the furnace 11 a short distance, depending entirely upou the size of the box, that the lower part of the box, and particularly the pipe 9, may be heated throughout, as far as exposed in the furnace, to abright-red heat, especial care being exercised to see that the top of Athe pipeis so heated, as the cnrrents of gas tend to follow the upper side of There is a space of several inches above the pipe, and the brickwork behind it is set out to almost touch the pipe that the flame may be forced first under and then over drawing, which.

the top of the pipe to heat it suflicicntly and homogeneously. The box 8 is provided ,with a l'm-i'foratcdl support 13, upon which thc chemicals are placed that combine with or act upon thc sulphur and sulphur compounds when thc latter are sufficiently heated.

1t is the outlet to the pipe'15, through wh ich the oil-vapor passes to Vthe condenser to be liquefied. i

The operation is as follows: The oil to be desulphurized is put in the still 1. The alkali or alkaliestobe used maybe mixed with a little `plasterofparis, be properly dried, then cut or broken into small cubes or pieces, and placed on the supportl in box 8. As a rule, if two or more are used they are placed in layers alternately,l although not always. The auxiliary furnace is then fired up, and when the box 8 and pipe 9 begin to redden the fire under the still 1 is started. By the time the vapors begin to pass over thc part of the box and the pipe exposed in the furnace will be bright red. As the vaporsare discharged from the still 1 they carry with them more or less sulphur, and upon its admission into the red-hot pipe 9 the sulphur and sulphur compounds are heated to a degree above the boiling-point of sulphur or above 440" centigrade at the pressure of the atmosphere. This operates to vaporize the sulphur and to crack or split up the sulphur compounds, which pass while in this condition through the perforated support 13 into theinnnediate presence of and in contact with the alkali or alkalies, their hydrates (caustics) or carbonates, as the case may be, placed upon said support,uniting in box 8 with the chemicals placed therein, forming a new compound, from which the sulphur does not separate if the process of distillation is continued. The koil-vapor thus freed from sulphur then passes from said box 8 through its outlet 14 and pipe 15 to condensers, (not shown,) wherein it is liquefied. lThe' distillate thus desulphurized can then be treated by any of the welh known methods for treating petroleum distillate.

No special form of apparatus is requiredto carry out this process, the essential and imperative featuresbeing that the apparatus be of such form as to admit of thoroughly heating all of the oil-vapor passed through it to the temperature described and to expose the oil-vapor so heated to the. action of one or more alkalies, their hydrates (canstics) or carbonates. XVe prefer to carry out the process without pressure.

Having described our invention, what we claim as new, and desire to secure by Letters Patent of the United States, is-

1. The herein-described process of desulphurizin'g oil, which consists in vaporzng the oil containing sulphur or sulphur conipounds and heating the vaporized oil to a delOO IlO

480,312 l y. a

grec of heat at or above the boiling-point ofv Yaporized o il sohea'ted to the yaction' of anhyzo sulphur andjthen'exposing the vapoljized voil d-rated (caustic) alkali and chenv condensing so heated'to the yaction of one or more alkalies the oil-vapor. w

and then condensing the oil. .y OTT .AMENl-l consists in vaporiningthe oil containing sulphur or sulphurtcompounds and heating the n Witnesses: A vaporized oil co-agdegree of heat at or above ROBT.' FULLERTON,

2. The processofeslphuizing oil, which JOSIAH H MACY the boiling-point of sulphur and exposing the ANDREW SCHENCK. 

